EP3103654B2 - Mélange de caoutchouc et pneu de vehicule - Google Patents

Mélange de caoutchouc et pneu de vehicule Download PDF

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Publication number
EP3103654B2
EP3103654B2 EP16169820.4A EP16169820A EP3103654B2 EP 3103654 B2 EP3103654 B2 EP 3103654B2 EP 16169820 A EP16169820 A EP 16169820A EP 3103654 B2 EP3103654 B2 EP 3103654B2
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EP
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Prior art keywords
rubber
rubber mixture
phr
formula
group
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EP16169820.4A
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German (de)
English (en)
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EP3103654B1 (fr
EP3103654A1 (fr
Inventor
Viktoria Pavon Sierra
Norbert Müller
Catarina Sá
Thorsten Torbrügge
Christoph Vatterott
Anette Stark
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Continental Reifen Deutschland GmbH
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Continental Reifen Deutschland GmbH
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
    • B29B7/7476—Systems, i.e. flow charts or diagrams; Plants
    • B29B7/7495—Systems, i.e. flow charts or diagrams; Plants for mixing rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0016—Compositions of the tread
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/25—Incorporating silicon atoms into the molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/548—Silicon-containing compounds containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00—Compositions of rubber derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00—Compositions of natural rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/32—Properties characterising the ingredient of the composition containing low molecular weight liquid component
    • C08L2207/324—Liquid component is low molecular weight polymer

Definitions

  • the invention relates to a sulfur-crosslinkable rubber mixture, in particular for treads on vehicle tires, and a vehicle tire.
  • Liquid polybutadiene with high vinyl content and a high glass transition temperature (T g ) is used in the EP 1035164 A proposed for tire treads as a replacement for conventional plasticizer oils.
  • T g glass transition temperature
  • the DE 102008058996 A1 and the DE102008058991 A1 disclose amine-end-modified liquid polybutadienes or carboxyl-end-modified liquid polybutadienes in tread mixtures with a high amount of synthetic rubber as a replacement for common plasticizer oils.
  • the tires should be characterized by a very good balance between low fuel consumption and good grip properties and the ability to suppress cracking at the bottom of tread grooves while maintaining wear resistance.
  • the EP 2060604 B1 discloses a rubber mixture containing a functionalized polymer with an Mw of 20,000 g/mol and carbon black as a filler in combination with 60 phr of natural rubber.
  • a polybutadiene modified with triethoxysilane is used instead of a silane in an NR-free rubber mixture based on synthetic rubber and silica as a filler.
  • the JP2013082771 discloses a combination of two modified diene rubbers A and B, each of which has modifications.
  • the modified diene rubbers A and B represent solid rubbers due to their weight average molecular weight (at room temperature).
  • the JP2014080504 discloses a modified silica, wherein the surface of the silica can be modified with a modified liquid polybutadiene and with a sulfur-containing silane and optionally with an aminosilane.
  • a rubber mixture In addition to the requirements for the physical properties mentioned, a rubber mixture must also be designed in such a way that products made from it, such as a vehicle tire, can be manufactured as easily as possible.
  • the heating kinetics of the rubber mixture play an important role in its industrializability.
  • a crucial aspect is the duration of the necessary heating of the rubber mixture and thus the tire for vulcanization during the manufacturing process. Heating the tire for longer causes higher energy consumption, while heating for too short a time leads to insufficient cross-linking of the polymer chains, which means that the structural durability during driving is not guaranteed. It is also unfavorable if only one component requires prolonged heating, as other components are overheated and a so-called reversion can occur.
  • the resulting sulfur bridges between the polymers are partially broken down again, which in turn results in poorer durability.
  • the goal is therefore to design the tire with its various components in such a way that all components are heated as optimally as possible with the lowest possible energy consumption.
  • the rapid crosslinkability for low energy consumption is limited by the production process of the individual rubber mixtures, as extrusion through templates causes an increase in temperature to form individual components. This can lead to what is known as “scorching” of a mixture, i.e. early, undesirable pre-crosslinking.
  • the present invention is therefore based on the object of providing a sulfur-crosslinkable rubber mixture which enables an improvement in rolling resistance while maintaining the same other tire properties, and in addition the heating times should be improved so that a moderate time for heating out the tire is possible without a simultaneous susceptibility to scorch becomes.
  • the rubber mixture according to the invention has improved rolling resistance behavior with the other tire properties remaining the same and an equal or increased vulcanization time t 10 as well as a reduction in the vulcanization times t 90 and t 95 . It is therefore possible to use the rubber mixture to produce products such as pneumatic vehicle tires that can be baked cost-effectively without having to accept the risk of overheating other components. This enables economically sensible processing of the rubber mixture according to the invention while at the same time ensuring process reliability, since the rubber mixture is not susceptible to scorch.
  • a further object on which the present invention is based is to provide a vehicle tire which has a lower (and therefore improved) rolling resistance and at the same time can be produced more cost-effectively and in a more energy-saving manner, without the other tire properties being significantly negatively affected.
  • the problem is solved in that the vehicle tire has at least one vulcanizate of at least one sulfur-crosslinkable rubber mixture with the above features in at least one component.
  • the vehicle tire preferably has the rubber mixture at least in the tread, and here preferably in the cap in the case of a tread with a cap/base construction.
  • cap is to be understood as meaning the part of the tread that comes into contact with the road and is arranged radially on the outside (tread top part or tread cap).
  • base is to be understood as meaning the part of the tread that is arranged radially on the inside and therefore does not come into contact with the road during driving or only at the end of the tire's life (tread lower part or tire base).
  • vehicle tires are understood to mean pneumatic vehicle tires and solid rubber tires, including tires for industrial and construction site vehicles, truck, car and bicycle tires.
  • the rubber mixture according to the invention is also suitable for treads which consist of different tread mixtures arranged next to one another and/or one below the other (multi-component treads).
  • the rubber mixture according to the invention is also suitable for other technical rubber articles, such as bellows, conveyor belts, air springs, belts, straps or hoses, and shoe soles.
  • the specification phr (parts per parts of rubber by weight) used in this document is the usual quantity specification for mixture recipes.
  • the dosage parts by weight of the individual substances in this document is 100 parts by weight of the total mass of all high molecular weight and therefore solid rubbers present in the mixture.
  • the polybutadiene contained according to the invention with Mw of 500 to 12,000 g/mol is therefore not included as rubber in a hundred parts of the phr calculation.
  • the specification phf (parts per hundred parts of filler by weight) used in this document is the quantity specification for coupling agents for fillers commonly used in the rubber industry.
  • phf refers to the silica present, which means that other fillers that may be present, such as carbon black, are not included in the calculation of the amount of silane.
  • GPC gel permeation chromatography
  • THF tetrahydrofuran
  • the sulfur-crosslinkable rubber mixture contains at least one liquid polybutadiene, which is terminally modified with organosilicon and has a weight average Mw of the molecular weight according to GPC of 500 to 12,000 g/mol.
  • the value range of the Mw includes that it is a liquid polybutadiene at room temperature.
  • the short term “liquid polybutadiene” is therefore also used in the context of the present invention.
  • the Mw information refers to the polybutadiene including the organosilicon modification.
  • the liquid polybutadiene is modified with at least one radical according to formula I): I) (R 1 R 2 R 3 ) Si- where R 1 , R 2 , R 3 can be the same or different in the structures and can be selected from linear or branched alkoxy, cycloalkoxy, alkyl, cycloalkyl or aryl groups with 1 to 20 carbon atoms, and where the remainder is according to formula I) is connected directly or via a bridge to the polymer chain of the polybutadiene and wherein the bridge consists of a saturated or unsaturated carbon chain, which can also contain cyclic and / or aliphatic and / or aromatic elements as well as heteroatoms in or on the chain.
  • all groups R 1 , R 2 , R 3 are alkoxy groups. Particularly preferably, at least one of the three groups R 1 , R 2 , R 3 is an ethoxy group. Very particularly preferably, all three groups R 1 , R 2 , R 3 are each an ethoxy group (abbreviated to OEt). This applies to all mentioned embodiments of the invention including formulas II) and III).
  • the remainder according to formula I) is not connected directly, but via a bridge.
  • a residue including a bridge according to formula II) is preferably bound to the polymer chain of the polybutadiene.
  • urethane is understood to mean a group -N(H)-C(O)-O-.
  • PB polybutadiene and therefore represents the polymer chain of the monomers.
  • the liquid polybutadiene has an Mw of 500 to 12,000 g/mol. This results in very good properties in terms of rolling resistance and processability, as Mw below 12,000 allow liquid dosage due to the low viscosities.
  • the liquid polybutadiene particularly preferably has an Mw of 1000 to 9000 g/mol. This in turn results in particularly good properties in terms of rolling resistance and processability.
  • the liquid polybutadiene preferably has a glass transition temperature T g according to DSC (Mettler Toledo apparatus; measurement from +70 ° C to -150 ° C, temperature change of 10 K/min; determination of the glass transition point analogous to ISO-FDIS 11357-2) from -85 to -30 °C, particularly preferably -60 to -40 °C. This results in particularly good rolling resistance indicators.
  • DSC Metal Organic Chemical Vapor Determination temperature
  • the liquid polybutadiene preferably has a vinyl content (content of 1,2-bonded butadiene, based on the monomers of the polymer chain of the polybutadiene) of 40 to 75%, particularly preferably 50 to 75%, very particularly preferably 55 to 70%.
  • the liquid polybutadiene preferably has a 1,4-trans content of 5 to 30% (based on the monomers of the polymer chain of the polybutadiene), particularly preferably 10 to 25%.
  • the cis portion of the liquid polybutadiene is preferably 5 to 30% (based on the monomers of the polymer chain of the polybutadiene), particularly preferably 10 to 25%.
  • microstructure such as 1,4-trans portion, vinyl content, cis portion are determined after the liquid polybutadiene has been synthesized (see below) using 13 C-NMR (90.5628 MHz; relaxation agent Cr(acac) 3 ; Solvent CDCl 3 , Bruker 360 MHz).
  • the liquid polybutadiene can be produced, for example, by reacting 3-isocyant-n-propyl-triethoxysilane with terminally hydroxy-functionalized polybutadiene (e.g. Krasol LBH-P3000) as in US 2002/0082333 A1 described.
  • 3-isocyant-n-propyl-triethoxysilane e.g. Krasol LBH-P3000
  • terminally hydroxy-functionalized polybutadiene e.g. Krasol LBH-P3000
  • the amount of liquid polybutadiene is 1 to 40 phr, preferably 2 to 17 phr, particularly preferably 5 to 15 phr.
  • the task of improving the trade-off between rolling resistance and tear properties and good processability is achieved particularly well.
  • the rubber mixture according to the invention contains at least one diene rubber with a comparatively high molecular weight in contrast to liquid polybutadiene, namely a weight average Mw of the molecular weight according to GPC of 250,000 to 5,000,000 g / mol.
  • This at least one diene rubber represents the high molecular weight rubber component, which represents the hundred parts in the calculation of the phr reference value, although a mixture of different diene rubbers, as described below, is also conceivable and the sum of all high molecular weight diene rubbers results in 100 phr.
  • the at least one diene rubber is natural polyisoprene and/or synthetic polyisoprene and/or polybutadiene (butadiene rubber) and/or styrene-butadiene copolymer (styrene-butadiene rubber) and/or epoxidized polyisoprene and/or styrene rubber.
  • nitrile rubber hydrogenated acrylonitrile butadiene rubber, chloroprene rubber, butyl rubber, halobutyl rubber or ethylene-propylene-diene rubber are used in the production of technical rubber articles, such as belts, belts and hoses, and/or shoe soles.
  • the diene rubber(s) is preferably natural polyisoprene (NR) and/or synthetic polyisoprene (IR) and/or polybutadiene (BR, butadiene rubber) and/or styrene-butadiene copolymer (SBR, styrene -butadiene rubber).
  • NR natural polyisoprene
  • IR synthetic polyisoprene
  • BR polybutadiene
  • SBR styrene-butadiene copolymer
  • the natural and/or synthetic polyisoprene can be both cis-1,4-polyisoprene and 3,4-polyisoprene.
  • the use of cis-1,4-polyisoprene with a cis 1.4 proportion > 90% by weight is preferred.
  • such a polyisoprene can be obtained by stereospecific polymerization in solution with Ziegler-Natta catalysts or using finely divided lithium alkyls.
  • natural rubber (NR) is a cis-1,4 polyisoprene; the cis-1,4 content in natural rubber is greater than 99% by weight.
  • the natural and/or synthetic polyisoprene preferably has a weight-average molecular weight Mw according to GPC of 250,000 to 5,000,000 g/mol and, according to the invention, is therefore one of the high-molecular rubbers which are included in the hundreds of parts when calculating the phr reference value.
  • the styrene-butadiene rubber can be both solution-polymerized styrene-butadiene rubber (SSBR) and emulsion-polymerized styrene-butadiene rubber (ESBR), including a mixture of at least one SSBR and at least one ESBR can be used.
  • SSBR solution-polymerized styrene-butadiene rubber
  • ESBR emulsion-polymerized styrene-butadiene rubber
  • styrene-butadiene rubber and “styrene-butadiene copolymer” are used synonymously in the context of the present invention. In any case, preference is given to styrene-butadiene copolymers with an Mw of 250,000 to 600,000 g/mol (two hundred fifty thousand to six hundred thousand grams per mole).
  • the styrene-butadiene copolymer(s) used can be end group modified with modifications and functionalizations and/or functionalized along the polymer chains.
  • modifications and functionalizations and/or functionalized along the polymer chains When modifying can they are those with hydroxy groups and/or ethoxy groups and/or epoxy groups and/or siloxane groups and/or amino groups and/or aminosiloxane and/or carboxy groups and/or phthalocyanine groups and/ or silane sulfide groups.
  • modifications known to those skilled in the art, also referred to as functionalizations are also possible.
  • Metal atoms can be part of such functionalizations.
  • a low-cis polybutadiene is, for example, Li-BR (lithium-catalyzed butadiene rubber) with a cis content of 20 to 50% by weight. With a high-cis BR, particularly good abrasion properties and low hysteresis of the rubber mixture are achieved.
  • the polybutadiene used can be end-group modified and/or functionalized along the polymer chains using the modifications and functionalizations mentioned above for the styrene-butadiene rubber.
  • the rubber mixture contains 3 to 15 phf, preferably 4.5 to 12 phf, of at least one blocked mercaptosilane.
  • Unblocked mercaptosilanes are silanes that have an -S-H group, i.e. a hydrogen atom on the sulfur atom.
  • Blocked mercaptosilanes are silanes that have an S-SG group, where SG is the abbreviation for a protective group on the sulfur atom.
  • Protective groups according to the invention are, as explained below, acyl groups. It is clear to the person skilled in the art that this information refers to the initial state of the components of the sulfur-crosslinkable rubber mixture and that during the mixing process and/or vulcanization the protective groups are split off and the respective sulfur atoms react chemically.
  • Blocked mercaptosilanes have a protecting group on the sulfur atom, in the present case the group R 5 in formula IV), which means they are also called “protected mercaptosilanes”.
  • the mercaptosilane is the blocked mercaptosilane 3-octanoylthio-1-propyltriethoxysilane, whereby in formula IV) above, all R 4 radicals are ethoxy (OEt) and Z is a propyl group and R 5 is an octanoyl group is.
  • the rubber mixture according to the invention can further contain other silanes known in the art, such as TESPD (3,3'-bis(triethoxysilylpropyl) disulfide) or TESPT (3,3'-bis(triethoxysilylpropyl) tetrasulfide) or octyltriethoxysilanes (e.g. Si208® , Co . Evonik).
  • silanes known in the art, such as TESPD (3,3'-bis(triethoxysilylpropyl) disulfide) or TESPT (3,3'-bis(triethoxysilylpropyl) tetrasulfide) or octyltriethoxysilanes (e.g. Si208® , Co . Evonik).
  • silane preferably contains no other silane apart from the mercaptosilane, ie it is preferably free of other silanes such as TESPD (3,3'-bis(triethoxysilylpropyl) disulfide) or TESPT (3,3'-bis(triethoxysilylpropyl) tetrasulfide) or octyltriethoxysilane ( e.g. Si208 ® , Evonik).
  • TESPD 3,3'-bis(triethoxysilylpropyl) disulfide
  • TESPT 3,3'-bis(triethoxysilylpropyl) tetrasulfide
  • octyltriethoxysilane e.g. Si208 ® , Evonik
  • the rubber mixture according to the invention contains at least one silica.
  • the rubber mixture preferably contains 20 to 200 phr, particularly preferably 40 to 165 phr, of at least one silica.
  • the rubber mixture contains 70 to 100 phr of at least one silica.
  • the rubber mixture contains 90 to 120 phr of at least one silica.
  • silicic acid and “silica” are used synonymously in the context of the present invention, as is also customary in the professional world.
  • the silicas can be the silicas known to those skilled in the art, which are used as a filler for tire rubber compounds are suitable to act. However, it is particularly preferred if a finely divided, precipitated silica is used which has a nitrogen surface (BET surface) (according to DIN ISO 9277 and DIN 66132) of 35 to 350 m 2 /g, preferably from 60 to 260 m 2 /g, particularly preferably from 120 to 230 m 2 /g, and a CTAB surface area (according to ASTMD 3765) from 30 to 400 m 2 /g, preferably from 60 to 250 m 2 /g, particularly preferably from 120 to 230 m 2 /g.
  • BET surface nitrogen surface
  • CTAB surface area accordinging to ASTMD 3765
  • the vulcanizates have particularly good physical properties.
  • Silicas can therefore be used, for example: B. both those of the type Ultrasil ® VN3 (trade name) from Evonik as well as highly dispersible silicas, so-called HD silicas (e.g. Zeosil ® 1165 MP from Solvay), can be used.
  • the rubber mixture according to the invention is free of soot, i.e. it contains 0 phr of soot.
  • it can further contain at least one carbon black in amounts of 0.1 to 30 phr, preferably 0.1 to 10 phr, particularly preferably 0.1 to 5 phr. If carbon black is included, a small amount of 0.1 to 5 phr is particularly preferred for improved rolling resistance indicators.
  • soot all types of soot known to those skilled in the art are conceivable.
  • a carbon black which has an iodine adsorption number according to ASTM D 1510 of 30 to 180 g/kg, preferably 30 to 130 kg/g, and a DBP number according to ASTM D 2414 of 80 to 200 ml/100 g, preferably 100 to 200 ml/100g, particularly preferably 100 to 180 ml/100g.
  • the rubber mixture according to the invention can also contain other known polar and/or non-polar fillers, such as aluminosilicates, chalk, starch, magnesium oxide, titanium dioxide or rubber gels.
  • polar and/or non-polar fillers such as aluminosilicates, chalk, starch, magnesium oxide, titanium dioxide or rubber gels.
  • carbon nanotubes including discrete CNTs, so-called hollow carbon fibers (HCF) and modified CNT containing one or more functional groups, such as hydroxy, carboxy and carbonyl groups
  • CNT carbon nanotubes
  • HCF hollow carbon fibers
  • modified CNT containing one or more functional groups, such as hydroxy, carboxy and carbonyl groups are conceivable.
  • Graphite and graphene as well as so-called “carbon-silica dual-phase fillers” are also conceivable as fillers.
  • Zinc oxide is not one of the fillers in the context of the present invention.
  • the rubber mixture contains at least one plasticizer (in addition to the liquid polybutadiene mentioned), the total amount of plasticizer preferably being 1 to 90 phr, particularly preferably 5 to 70 phr, very particularly preferably 15 to 60 phr, is.
  • the total amount of plasticizer preferably being 1 to 90 phr, particularly preferably 5 to 70 phr, very particularly preferably 15 to 60 phr, is.
  • plasticizers used in the context of the present invention include all plasticizers known to those skilled in the art, such as aromatic, naphthenic or paraffinic mineral oil plasticizers, such as MES (mild extraction solvate) or RAE (Residual Aromatic Extract) or TDAE (treated distillate aromatic extract), or rubber to-liquid oils (RTL) or biomass-to-liquid oils (BTL) preferably with a content of polycyclic aromatics of less than 3% by weight according to method IP 346 or rapeseed oil or facts or plasticizer resins that do not belong to the above
  • MES mid extraction solvate
  • RAE Residual Aromatic Extract
  • TDAE treated distillate aromatic extract
  • RTL rubber to-liquid oils
  • BTL biomass-to-liquid oils
  • plasticizer resins that do not belong to the above
  • adhesive resins mentioned, or liquid polymers that do not correspond to the modified liquid polybutadiene described above and whose average molecular weight (determined by GPC gel permeation chromat
  • the plasticizer is preferably selected from the group consisting of the plasticizers mentioned above. Mineral oils are particularly preferred as plasticizers.
  • mineral oil this is preferably selected from the group consisting of DAE (Distilled Aromatic Extracts) and/or RAE (Residual Aromatic Extract) and/or TDAE (Treated Distilled Aromatic Extracts) and/or MES (Mild Extracted Solvents) and /or naphthenic oils.
  • DAE Disistilled Aromatic Extracts
  • RAE Residual Aromatic Extract
  • TDAE Temporal Distilled Aromatic Extracts
  • MES Mild Extracted Solvents
  • the plasticizer(s) are preferably added in at least one basic mixing stage.
  • the proportion of the total amount of further additives is 3 to 150 phr, preferably 3 to 100 phr and particularly preferably 5 to 80 phr.
  • the total proportion of the other additives contains 0.1 to 10 phr, preferably 1 to 8 phr, particularly preferably 1.5 to 4 phr, zinc oxide (ZnO).
  • the conventionally used zinc oxide generally has a BET surface area of less than 10 m 2 /g.
  • a zinc oxide with a BET surface area of 10 to 100 m 2 /g such as so-called “nano-zinc oxides”, can also be used.
  • the rubber mixture can also contain adhesive systems such as cobalt salts and reinforcing resins (e.g. resorcinol-HMMM/HMT) for use in body mixtures, especially rubber coating mixtures.
  • adhesive systems such as cobalt salts and reinforcing resins (e.g. resorcinol-HMMM/HMT) for use in body mixtures, especially rubber coating mixtures.
  • the vulcanization of the sulfur-crosslinkable rubber mixture according to the invention is carried out in the presence of sulfur and/or sulfur donors with the aid of vulcanization accelerators, whereby some vulcanization accelerators can also act as sulfur donors.
  • the accelerator is selected from the group consisting of thiazole accelerators and/or mercapto accelerators and/or sulfenamide accelerators and/or thiocarbamate accelerators and/or thiuram accelerators and/or thiophosphate accelerators and/or thiourea accelerators and/or xanthate accelerators and/or guanidine accelerators.
  • a sulfenamide accelerator which is selected from the group consisting of N-cyclohexyl-2-benzothiazolesufenamide (CBS) and/or N,N-dicyclohexylbenzothiazole-2-sulfenamide (DCBS) and/or benzothiazyl-2-sulfenemorpholide (MBS ) and/or N-tert-butyl-2-benzothiazylsulfenamide (TBBS).
  • CBS N-cyclohexyl-2-benzothiazolesufenamide
  • DCBS N,N-dicyclohexylbenzothiazole-2-sulfenamide
  • MFS benzothiazyl-2-sulfenemorpholide
  • TBBS N-tert-butyl-2-benzothiazylsulfenamide
  • sulfur-donating substances known to those skilled in the art can be used as the sulfur-donating substance.
  • this is preferably selected from the group containing, for example, thiuram disulfides, such as tetrabenzylthiuram disulfide (TBzTD) and/or tetramethylthiuram disulfide (TMTD) and/or tetraethylthiuram disulfide (TETD), and/or thiuram tetrasulfides, such as dipentamethylenethiuram tetrasulfide (DP TT) , and/or dithiophosphates, such as e.g.
  • DipDis bis-(diisopropyl)thiophosphoryl disulfide) and/or bis(O,O-2-ethylhexyl-thiophosphoryl)polysulfide (e.g. Rhenocure SDT 50 ® , Rheinchemie GmbH) and/or zinc dichloryl dithiophosphate (e.g. Rhenocure ZDT/ S ® , Rheinchemie GmbH) and/or zinc alkyl dithiophosphate, and/or 1,6-bis(N,N-dibenzylthiocarbamoyldithio)hexane and/or diaryl polysulfides and/or dialkyl polysulfides.
  • Bis-(diisopropyl)thiophosphoryl disulfide) and/or bis(O,O-2-ethylhexyl-thiophosphoryl)polysulfide e.g. Rhenocure SDT 50 ® , Rheinchemie GmbH
  • This system contains a vulcanization agent that crosslinks with a functionality greater than four and at least one vulcanization accelerator.
  • the vulcanizing agent that is crosslinked with a functionality of greater than four has, for example, the general formula A): A) G[C a H 2a -CH 2 -S b Y] c wherein G is a polyvalent cyclic hydrocarbon group and/or a polyvalent heterocarbon group and/or a polyvalent siloxane group containing 1 to 100 atoms; wherein each Y independently selected from a rubber-active group contains sulfur-containing functionalities; and where a, b and c are integers for which independently: a equals 0 to 6; b equals 0 to 8; and c is 3 to 5.
  • the rubber-active group is preferably selected from a thiosulfonate group, a dithiocarbamate group, a thiocarbonyl group, a mercapto group, a hydrocarbon group and a sodium thiosulfonate group (Bunte salt group).
  • sulfur and sulfur donors including sulfur-donating silanes such as TESPT, and vulcanization accelerators as described above and vulcanization agents that crosslink with a functionality greater than four, as in the WO 2010/049216 A2 described, such as a vulcanizing agent of the formula A), as well as the above-mentioned systems Vulkuren ® , Duralink ® and Perkalink ® conceptually summarized as vulcanizing agents.
  • the rubber mixture according to the invention preferably contains at least one vulcanizing agent during its production selected from the group containing, particularly preferably consisting of, sulfur and/or sulfur donors and/or vulcanization accelerators and/or vulcanization agents that crosslink with a functionality greater than four, added in the final mixing stage.
  • at least one vulcanizing agent during its production selected from the group containing, particularly preferably consisting of, sulfur and/or sulfur donors and/or vulcanization accelerators and/or vulcanization agents that crosslink with a functionality greater than four, added in the final mixing stage.
  • the use of the accelerators TBBS and/or CBS and/or diphenylguanidine (DPG) is particularly preferred.
  • vulcanization retarders may be present in the rubber mixture.
  • the sulfur-crosslinkable rubber mixture according to the invention is produced according to the process common in the rubber industry, in which a basic mixture with all components except the vulcanization system (sulfur and substances influencing vulcanization) is first produced in one or more mixing stages.
  • the finished mixture is created by adding the vulcanization system in a final mixing stage.
  • the finished mixture is further processed, for example, by an extrusion process and brought into the appropriate shape. Further processing then takes place by vulcanization, with sulfur crosslinking taking place due to the vulcanization system added in the context of the present invention.
  • the rubber mixture according to the invention described above is particularly suitable for use in vehicle tires, in particular pneumatic vehicle tires.
  • vehicle tires in particular pneumatic vehicle tires.
  • the application is conceivable in all tire components, such as the tread and/or the sidewall and/or in at least one inner component.
  • the rubber mixtures for the inner components of a tire are referred to as body mixtures.
  • the inner tire components are essentially squeegee, sidewall, inner liner (inner layer), core profile, belt, shoulder, belt profile, carcass, bead reinforcer, bead profile, horn profile and bandage.
  • the rubber mixture according to the invention is preferably used in treads of vehicle tires, preferably at least in the cap of treads with a cap/base construction.
  • the mixture is preferably brought into the form of a tread, preferably at least into the form of a tread cap, as a ready-mix before vulcanization and applied as is known during the production of the vehicle tire blank.
  • the tread preferably at least the tread cap, can also be wound onto a blank tire in the form of a narrow strip of rubber mixture.
  • the rubber mixture according to the invention can be used for both the cap and the base.
  • the rubber mixture according to the invention for use as a body mixture in vehicle tires is produced as already described for the tread.
  • the difference lies in the shaping after the extrusion process or calendering of the mixture.
  • the resulting forms of the still unvulcanized rubber mixture for one or more different body mixtures are then used to build a green tire.
  • the extruded, still unvulcanized mixture is brought into the appropriate shape and, during or afterward, is often provided with reinforcements, for example synthetic fibers or steel cords. This usually results in a multi-layer structure consisting of one and/or several layers of rubber mixture, one and/or several layers of the same and/or different reinforcements and one and/or several further layers of the same and/or a different rubber mixture.
  • comparison mixtures are marked V
  • the mixtures according to the invention are marked E.
  • the terminally organosilicon-modified liquid polybutadiene was prepared by reacting 3-isocyant-n-propyl-triethoxysilane with terminally hydroxy-functionalized polybutadiene (Krasol LBH-P3000), analogous to the description in US 2002/0082333 A1 , paragraph [0053], using 155 g of 3-isocyant-n-propyltriethoxysilane per kg of Krasol LBH-P3000. The reaction was carried out at 80 °C in a 5L (liter) reactor.
  • the mixture was produced according to the procedure common in the rubber industry under usual conditions in three stages in a laboratory mixer in which all components except the vulcanization system (sulfur and substances influencing vulcanization) were mixed in the first mixing stage (basic mixing stage). In the second mixing stage, the basic mixture was mixed again. The finished mixture was produced by adding the vulcanization system in the third stage (finished mixing stage), with mixing at 90 to 120 °C.
  • NR Natural rubber TSR
  • SBR SSBR, SLR 4601, Trinseo
  • Plasticizer 5 phr rapeseed oil + 20 phr MES f) Additives: 5, 2 phr anti-aging agents (DTPD, 6PPD, TMQ), 2 phr ozone protection wax, 2 phr zinc oxide (ZnO), 1 phr stearic acid, 4 phr processing aids (fatty acid esters and zinc soaps)
  • S 2 -Silane TESPD, JH-
  • the vulcanization times are reduced with the rubber mixtures E1 and E2 according to the invention through the combination of organosilicon-modified liquid polybutadiene and mercaptosilane, although this is not due to the individual measures (see V2 and V3 or V5 and V6). would have been expected.
  • the rolling resistance indicators especially the rebound elasticities at 70 ° C, improve.
  • the above-mentioned combination of components therefore surprisingly shows a synergistic interaction with regard to improving rolling resistance and heating times while maintaining the same other tire properties.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (9)

  1. Mélange de caoutchouc réticulable par le soufre, contenant
    - au moins un caoutchouc diénique et
    - au moins une silice et
    - 3 à 15 pcc d'au moins un mercaptosilane bloqué, des mercaptosilanes bloqués présentant un groupe protecteur sur l'atome de soufre, les groupes protecteurs étant des groupes acyles, et
    - 1 à 40 pcc d'au moins un polybutadiène liquide, qui est modifié par organosilicium en position terminale et qui présente une moyenne pondérale Mw du poids moléculaire selon la CPG de 500 à 12.000 g/mole, le polybutadiène liquide étant modifié par au moins un radical selon la formule I) :

            I)     (R1R2R3) Si-

    R1, R2, R3, dans les structures, pouvant être identiques ou différents et pouvant être choisis parmi les groupes alcoxy, alkyle, linéaires ou ramifiés, cycloalcoxy, cycloalkyle ou aryle, comprenant 1 à 20 atomes de carbone et le radical selon la formule I) étant lié directement ou via un pont à la chaîne polymère du polybutadiène et le pont étant constitué par une chaîne carbonée saturée ou insaturée qui peut également contenir des éléments cycliques et/ou aliphatiques et/ou aromatiques ainsi que, dans ou sur la chaîne carbonée, des hétéroatomes.
  2. Mélange de caoutchouc selon la revendication 1, caractérisé en ce que le radical selon la formule I) n'est pas lié directement mais via un pont selon la formule II) :

            II)     (R1R2R3)Si-Y-X-,

    dans la formule II), Y représentant une chaîne alkyle (-CH2)n- où n = 1 à 8 et X représentant un groupe fonctionnel qui est choisi dans le groupe constitué par ester, éther, uréthane, urée, amine, amide, thioéther, thioester.
  3. Mélange de caoutchouc selon la revendication 2, caractérisé en ce que le polybutadiène liquide modifié par organosilicium présente une structure selon la formule III) :
    Figure imgb0004
  4. Mélange de caoutchouc selon au moins l'une quelconque des revendications précédentes, caractérisé en ce que le polybutadiène liquide présentant une modification par organosilicium en position terminale présente une température de transition vitreuse Tg selon la DSC (calorimétrie différentielle à balayage) de -85 à -30°C.
  5. Mélange de caoutchouc selon au moins l'une quelconque des revendications précédentes, caractérisé en ce qu'il contient 2 à 17 pcc du polybutadiène liquide qui est modifié par organosilicium en position terminale.
  6. Mélange de caoutchouc selon au moins l'une quelconque des revendications précédentes, caractérisé en ce que le mercaptosilane bloqué présente la formule brute générale IV) :

            IV)     (R4)3Si-Z-S-R5,

    les radicaux R4 au sein d'une molécule pouvant être identiques ou différents les uns des autres et représentant des groupes alcoxy comprenant 1 à 10 atomes de carbone et
    R5 signifiant un groupe acyle comprenant 1 à 20 atomes de carbone et
    Z représentant un groupe alkyle comprenant 1 à 10 atomes de carbone.
  7. Mélange de caoutchouc selon la revendication 6, caractérisé en ce qu'il s'agit, pour le mercaptosilane, du mercaptosilane bloqué 3-octanoylthio-1-propyltriéthoxysilane.
  8. Pneu de véhicule qui présente au moins un élément qui est constitué, du moins en partie, par un mélange de caoutchouc vulcanisable par le soufre selon au moins l'une quelconque des revendications 1 à 7.
  9. Pneu pour véhicule selon la revendication 8, caractérisé en ce qu'il s'agit, pour l'élément, au moins de la bande de roulement.
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DE102015210423A1 (de) 2016-12-08

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